Heterocumulene Sulfinyl Radical OCNSO

Abstract

Neutral five-atomic cumulenes formally consisting of two pseudohalogens (e.g.,NCO,NNN,NSO) by sharing the central nitrogen atom are exotic species that have been barely studied. Through flash vacuum pyrolysis of CF 3 S(O)NCO at ca. 1200 K, sulfinyl isocyanate,bearing resonance structures of O=CÀN=S=Oa nd O=C=NÀS=O, has been generated in the gas phase and subsequently characterized in cryogenic matrices (Ar and N 2 ). Its reversible conformational (syn and anti) interconversion and photodecomposition were observed.Smallinorganicmoleculesbearingmultiple-bondingC, O, S, Na toms are of astrochemical and biological relevance that have been the targets of numerous experimental and theoretical studies. [1] Particularly,s imple species consisting of the triatomic pseudohalogens NNN and NCO are of fundamental importance due to interesting structural, conformational, and bonding properties.F or instances,t he exotic high-energy polynitrogen species N 4 , [2] N 5 , [3] N 6 , [4] and their respective isoelectronic analogues NNCO, [5] OCNCO, [6] and OCNNCO [7] /OCNNNN [8] have attracted great interest in the recent few decades.D espite the challenges facing the synthesis and characterization due to the metastability and the lack of synthetic method, significant progress has been made in the generation and direct observation of the four-and six-atomic species with various spectroscopic techniques. However,t he existence of the five-atomic cumulene species (N 5 and OCNCO) has not yet been proved experimentally, although the salts of the cations N 5 +[9] and OCNCO + , [10] as well as the one-electron-less interpseudohalogen NCNCO/ NCCNO [11] have been synthesized and structurally characterized.

Decomposition of Sulfonyl Azide Isocyanate and Sulfonyl Diazide: The Oxygen-Shifted Curtius Rearrangement via Sulfonyl Nitrenes

“…Given the previously observed rearrangement of sulfonyl nitrenes FS(O) 2 N 55 and CF 3 S(O) 2 N 24 to nitroso compounds FS(O)NO and CF 3 S-(O)NO, the presence of NO likely results from the decomposition of the analogous rearrangement product ((OCN)S(O)NO) of the putative nitrene intermediate OCNS(O) 2 N under the pyrolysis conditions. As a support of this assumption, the remaining fragments CN and SO 2 of (OCN)S(O)NO were indeed detected, whereas the thermally persistent radical OCNSO 56 was not observed.…”

Clean and Efficient Transformation of CO2 to Isocyanic Acid: The Important Role of Triatomic Cation ScNH+

“…8,9 In addition, the NCO unit is also an important building block in the field of pseudohalogen chemistry. 10,11 Moreover, the conjugate acid of NCO − , isocyanic acid (HNCO), is the simplest compound, possessing four main biogenic elements, and it was one of the first polyatomic molecules observed in the interstellar gas. It is highly desirable to develop a simple HNCO-producing reaction with high selectivity and reactivity by using CO 2 as the source and to understand the reaction mechanism.…”